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The synaptic vesicle membrane protein Synaptotagmin I may function as a Ca(super2+) sensor in neurotransmitter release. It contains two C(sub2)-domains that bind Ca(super2+). The mechanisms involved in Ca(super2+) dependent phospholipid binding by the C(sub2)A-domain of synaptotagmin I have been investigated. Data shows that negatively charged liposomes are bound by the C(sub2)A-domain in an electrostatic interaction. A molecular picture of interaction between a C(sub2)-domain and phospholipids is observed.

A unique fluorescent probe with n,pi* configuration, the azoalkane 2,3-diazabicyclo(2.2.2)oct-2-ene (DBO), is responsive to complexation by supramolecular hosts. The n,pi* fluorescent probe provides structural and kinetic data on host-guest complexation. The analysis of the complexation dynamics at high guest (DBO) concentration showed an unprecedented behavior, which may be indicative of singlet energy transfer between the free DBO and the CD*DBO complex.

Effects of three different organic acids including racemicmalicacid, succinic acid, and citric acid, which act as an impurity onthe solubility and metastable zone width of zinc lactate (ZnL2), have been studied. The results show that the presence ofall examined impurities increases the solution solubility and thevalues of solubility increase with increasing impurity concentration.The introduction of impurity also leads to a reduction on the metastablezone width, and the reductions are pronounced when the impurity concentrationincreased. Further, experimental data of metastable zone width wereanalyzed using the expression of the Nývlt’s approachand self-consistent Nývlt-like approach, which can be expressedin the form: ln(ΔTmax/T0) = Φ + β ln b, with interceptΦ = {(1 – m)/m}ln(ΔHd/RTlim) + (1/m)ln(f/KT0)and slope β = 1/m. Here T0and Tlimare the saturation andnucleation temperature, respectively. mis the apparentnucleation order, and Kis a new nucleation constantrelated to the factor fdefined as the number ofstable nuclei per unit volume, ΔHd, the heat of dissolution and Rthe gas constant.Comparing to the former one, the latter approach provides a more satisfactoryestimation for the metastable zone width at varying saturation temperature T0. The constant β for specific systemreveals independence of the temperature, while the constant Φincreases with increasing saturation temperature. In addition, bothconstants are proportional to the impurity concentration. Crystalhabits of final products are also influenced in the presence of impurities,but the crystal structures are barely changed. [ABSTRACT FROM AUTHOR]

The solid–liquid phase equilibrium of d- and l-tartaric acid (TA) was investigated in this work.Based onthe solubility data, the dissolution enthalpy and entropy of the monohydrateracemic tartaric acid (race-TA) and enantiomer were calculated usingvan't Hoff plots. Binary melting point phase diagrams of d- and l-TA and ternary phase diagrams of d-TA/water/l-TA were also described. The results show that TA exhibitsa racemic compound behavior. Furthermore, the influence of temperatureon the eutectic points between enantiomer and racemic compounds wasinvestigated. Finally, the importance of solid–liquid equilibriumon the purification and separation of enantiomers was discussed. [ABSTRACT FROM AUTHOR]

The stoichiometries and binding constants of the host—guest complexes between the bicyclic azoalkanes 1–6 and α-, β-, and γ-cyclodextrins (CDs) and the induced circular dichroism (ICD) of the complexes were analyzed. Assisted by proximity relationships obtained from 2D ROESY NMR spectra, the signs and intensities of the ICD spectra are interpreted in terms of the solution structures (co-conformations) of the CD complexes. The ICD assignments are based on the orientation-intensity ICD rules of Harata and Kodaka, which relate the ICD signs and intensities to the relative orientation of the electric dipole transition moment of the n,π* azo chromophore to the CD axis. The influence of the size of the guest and the host is discussed and the effect of introducing an additional chromophore (either a phenyl or a second azo group) on the ICD spectra is demonstrated. [ABSTRACT FROM AUTHOR]

Cancer immunotherapies based on cytotoxic CD8 + T lymphocytes (CTLs) are highly promising for cancer treatment. The specific interaction between T-cell receptors and peptide-MHC-I complexes (pMHC-I) on cancer cell membranes critically determines their therapeutic outcomes. However, the lack of appropriate endogenous antigens for MHC-I presentation disables tumor recognition by CTLs. By devising three antigen-loaded self-assembling peptides of pY-K(Ag)-ERGD, pY-K(Ag)-E, and Y-K(Ag)-ERGD to noncovalently generate light-activatable supramolecular antigens at tumor sites in different manners, we report pY-K(Ag)-ERGD as a promising candidate to endow tumor cells with pMHC-I targets on demand. Specifically, pY-K(Ag)-ERGD first generates low-antigenic supramolecular antigens on cancer cell membranes, and a successive light pulse allows antigen payloads to efficiently release from the supramolecular scaffold, directly producing antigenic pMHC-I. Intravenous administration of pY-K(Ag)-ERGD enables light-controlled tumor inhibition when combined with adoptively transferred antigen-specific CTLs. Our strategy is feasible for broadening tumor antigen repertoires for T-cell immunotherapies and advancing precision-controlled T-cell immunotherapies.

Functional groups and small-molecule organic matter are two key parts of coal. To explore the microscopic mechanism underlying the synergistic effect of both parts on methane adsorption, the oxygen-containing (-OH, -COOH, and -C=O) and nitrogen-containing (-NH 2 ) functional groups and two common small molecular organic matter methylbenzene and tetrahydrofuran-2-alcohol in coal are selected. The quantum chemical meta-GGA functional method is used to optimize all structures. The electrostatic potential analyses, weak interaction analyses, and theory of atoms in molecules have been used to delve further into the nature of this synergistic effect. Our results show that functional groups inhibit methane adsorption by coal molecules, and the inhibition effect is enhanced in the presence of methylbenzene. Interestingly, the synergistic effects between functional groups and small molecular organic matter are changed from inhibition to promotion after introducing tetrahydrofuran-2-alcohol, wherein -COOH has the best synergistic effect. This work not only offers a theoretical foundation for exploring the synergistic effect of small molecular organic matter and functional groups on methane adsorption by coal molecules but also lays a foundation for further research on gas prevention and extraction., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Two-dimensional (2D) organic-inorganic hybrid perovskites (OIPs) have exhibited ideal prospects for perovskite photodetectors (PDs) owing to their remarkable environmental stability, tunable band gap, and structural diversity. However, most perovskites face the great challenge of a narrow spectral response. Integrating 2D OIPs with a suitable wide band gap semiconductor gives opportunities to broaden the response spectra. Here, a photodetector based on the BA 2 PbI 4 /GaN heterostructure with a broadband photoresponse covering from the ultraviolet (UV) to visible band is designed. We demonstrate that the device is capable of detecting in the UV region by p-GaN being integrated with BA 2 PbI 4 . The morphology and material optical properties of BA 2 PbI 4 are characterized by transmission electron microscopy (TEM) and photoluminescence (PL). Additionally, the current-voltage ( I - V ) characteristics and photoresponses of the BA 2 PbI 4 /GaN heterojunction photodetector are investigated. The response spectrum of the photodetector is broadened from the visible to UV region, exhibiting good rectifying behavior in the dark conditions and a broadband photoresponse from the UV to the visible region. Additionally, the energy band is used to analyze the current mechanism of the BA 2 PbI 4 /GaN heterojunction PD. This study is expected to provide a new insight of optoelectronic devices by integrating 2D OIPs such as BA 2 PbI 4 and wide-band-gap semiconductors such as GaN to broaden the response spectra.

A simple coumarin hydrazine Schiff base bearing a thioether recognition fragment (compound CBBS ) has been rationally designed and easily prepared. CBBS exhibited an excellent selectivity for Pd(II) and a low detection limit of 65 nM (S/N = 3). The fluorescence emission intensities of CBBS at 495 nm were linear to Pd(II) concentrations in a wide range from 0 to 80 μM. Moreover, CBBS has been well used in fluorescence imaging of Pd(II) in living A549 cells. CBBS as a simple coordination-based fluorescent probe will inspire the researchers to develop a polymer for selective detection and adsorption of Pd(II)., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

We reported the synthesis of a tris(triazolylmethyl)amine (TTA)-bridged organosilane, functioning as Cu(I)-stabilizing ligands, and the installation of this building block into the backbone of mesoporous organosilica nanoparticles (TTASi) by a sol-gel way. Upon coordinating with Cu(I), the mesoporous Cu I -TTASi, with a restricted metal active center inside the pore, functions as a molecular-sieve-typed nanoreactor to efficiently perform Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reactions on small-molecule substrates but fails to work on macromolecules larger than the pore diameter. As a proof of concept, we witnessed the advantages of selective nanoreactors in screening protein substrates for small molecules. Also, the robust Cu I -TTASi could be implanted into the body of animal models including zebrafish and mice as biorthogonal catalysts without apparent toxicity, extending its utilization in vivo ranging from fluorescent labeling to in situ drug synthesis.

The proto-oncogene serine/threonine-protein kinase PIM3 plays critical roles in cancer, and it has been extensively exploited as a drug target. Here, we investigated the quantitative changes in the cellular proteome and phosphoproteome in liver cancer cells overexpressing PIM3 to obtain a better understanding of the regulatory functions of PIM3 and the underlying molecular mechanisms. This work depicted the landscape of gene expression and protein phosphorylation potentially regulated by PIM3. A signaling network analysis showed that PIM3 may coordinate various cellular processes, for example, signal transduction, cell cycle, apoptosis, and so forth. Intriguingly, quantitative phosphoproteomics revealed that the PIM3 overexpression elevated the phosphorylation of multiple Rho GTPase modulators that target RhoA, a central modulator of cell movement. Further investigations confirmed that PIM3 activated RhoA to subsequently regulate cytoskeletal rearrangements and cell migration. Taken together, this study comprehensively mapped the proteome and phosphoproteome regulated by PIM3 and revealed its role in promoting liver cancer cell migration and invasion by modulating Rho GTPase signaling.

Homochiral strands of alternating alleno-acetylenes and phenanthroline ligands (P)-1 and (P2)-2, as well as their corresponding enantiomers, selectively assemble with the addition of silver(I) salt to yield dinuclear and trinuclear double helicates, respectively. Upon increasing the solvent polarity, the dinuclear and trinuclear helicates interlock to form a [2]catenane and bis[2]catenane, bearing 14 chirality elements, respectively. The solid-state structure of the [2]catenane reveals a nearly perfect fit of the interlocked strands, and the ECD spectra show a significant amplification of the chiroptical properties upon catenation, indicating stabilization of the helical secondary structure. Highly selective narcissistic self-sorting was demonstrated for a racemic mixture consisting of both short and long alleno-acetylenic strands, highlighting their potential for the preparation of linear catenanes of higher order.

The noncovalent interactions in host-guest complexes of α-cyclodextrin (α-CD) with a series of benzoic acid derivatives (RBA) were investigated by electrospray ionization tandem mass spectrometry and density functional theory (DFT) calculations. The 1:1 stoichiometry of the anionic host-guest complexes was unequivocally confirmed by their mass-to-charge ratios (m/z) and isotope patterns. Collision-induced dissociation experiments revealed exclusive fragmentation into [α-CD](-) and neutral RBA and afforded the gas-phase kinetic stability trend [α-CD·3,5-diMeBA](-) < [α-CD·3-MeBA](-) < [α-CD·BA](-) < [α-CD·3-OHBA](-) < [α-CD·3,5-diOHBA](-). This trend follows that of the gas-phase basicities of the guest anions used, indicating that host-guest pairs with more comparable basicities form more stable complexes. DFT calculations at the M06-L/6-31+G(d,p) level of theory provided detailed structural assignments and further elucidated the experimental observations, suggesting that the anionic [α-CD·RBA](-) inclusion complexes are favored over the nonspecific complexes in the gas phase and that hydrogen bonding constitutes the primary host-guest interaction. Additionally, the results provide an estimated gas-phase basicity ΔG(0) = 325-327 kcal mol(-1) for [α-CD](-).

A new C(2)-symmetric chiral bis-sulfoxide ligand, (R,R)-1,2-bis(tert-butylsulfinyl)benzene, has been designed and prepared by the reaction of (R)-benzyl tert-butylsulfoxide with (R)-thiosulfinate. This ligand exhibits excellent enantioselectivities in the Rh-catalyzed asymmetric 1,4-addition reaction. In particular, the present work has realized access to optically pure flavanones for the first time through 1,4-addition of arylboronic reagents to chromenones.

The binding of propylene oxide (PO) to a series of metal cations LM(III)(+), where for L = tetraphenylporphyrin (TPP) M = Al, Ga, Cr, and Co, and for L = (R,R)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexenediamine (salen) M = Al and Cr, was studied in the gas phase by electrospray tandem mass spectroscopy, and the relative stabilities of LM(PO)(2)(+) and LM(PO)(+) cations were determined. The chromium(III) and aluminum(III) cations most tenaciously bind PO, and for M = Al, coordination to the TPP ligated metal center was favored relative to salen. For (TPP)M(PO)(2)(+), the dissociation of PO followed the order M = Al > Cr, but for (TPP)M(PO)(+) the dissociation was M = Cr > Al. The single-crystal structural determinations on (R,R-salen)AlOCHMe(S)CH(2)Cl.0.5PO and (R,R-salen)AlO(2)CMe.1.5py grown in neat PO and pyridine, respectively, reveal five-coordinate aluminum(III) centers with the alkoxide/acetate ligands in the axial position of a square-based pyramid. These results are discussed in terms of the reactivity of these metal complexes in ring-opening polymerizations and copolymerizations with PO and CO(2), respectively.

The gas-phase reactions of a series of mass-selected mononuclear and dinuclear Cr(salen) complexes with propylene oxide suggest that the enhanced reactivity of the dinuclear complexes in gas-phase and in solution may derive from a dicationic mechanism in which the alkoxide chain is mu(2)-coordinated to two Lewis acidic metal centers. The double coordination is proposed to suppress backbiting, and hence chain-transfer in the gas-phase homopolymerization of epoxides.

Derivatives of the azoalkane 2,3-diazabicyclo[2,2,2]oct-2-ene (1a) with bridgehead 1,4-dialkyl (1b), 1,4-dichloro (1c), 1-hydroxymethyl (1d), 1-aminomethyl (1e), and 1-ammoniummethyl (1f) substituents form host-guest inclusion complexes with beta-cyclodextrin. They were employed as probes to assess substituent effects on the kinetics and thermodynamics of this complexation by using time-resolved and steady-state fluorimetry, UV spectrophotometry, induced circular dichroism (ICD) measurements, and (1)H NMR spectroscopy. The kinetic analysis based on quenching of the long-lived fluorescence of the azoalkanes by addition of host provided excited-state association rate constants between 2.6 x 10(8) and 7.0 x 10(8) M(-)(1) s(-)(1). The binding constants for 1a (1100 M(-1)), 1b (900 M(-1)), 1c (1900 M(-1)), 1d (180 M(-1)), 1e (250 M(-1)), and 1f (ca. 20 M(-1)) were obtained by UV, NMR, and ICD titrations. A positive ICD signal of the azo absorption around 370 nm was observed for the beta-cyclodextrin complexes of 1a, 1d, and 1f with the intensity order 1a >> 1d approximately 1f, and a negative signal was measured for those of 1b, 1c, and 1e with the intensity order 1c < 1b approximately 1e. The ICD was employed for the assignment of the solution structures of the complexes, in particular the relative orientation of the guest in the host (co-conformation).